Process of and apparatus for making carbon dioxide



(No Model.) 3 Sheets-Sheet 1.

S. OABOT.

PROGESS OF AND APPARATUS FOR MAKING CARBON DIOXIDE. No. 359,996. Patented Mar. 29, 1887.

de9bar/zegien WITNESSES 06/ Attorney u mans Pammm nmr. Wnidngtom a. c.

(No Model.) 3 Sheets-Sheet 2.

S. GABOT.

PROGESS OF AND APPARATUS FOR MAKING CARBON DIOXIDE.

No. 359,996. Patented Mar. 29, 1887.

WITNESSES .A, llgfim J JJVVEJVTOR d 06' WW5 W W W W Antoine;

N. PETERS. Pheko-Lilho3nphen mm ylcn, 0.5.

3 Sheets-Sheet 3.

(NoModeL) S. GABOT.

PROCESS OF AND APPARATUS FOR MAKING CARBON DIDXIDE. N0. 359,996. PatentedvMar. 29, 1887.

1NVEJvjbR N4 PEER PhuwUmograyImr, Washington, D. c

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SAMUEL GABOT, OF BOSTON, MASSACHUSETTS.

PROCESS OF AND APPARATUS FOR MAKING CARBON DIOXIDE.

SPECIFICATION forming part of Letters Patent No. 359,996, dated March 29, 1887.

Application filed July 15, ISFG. Serial No. 208,164. (No model.)

To aZZ whom it may concern.-

Be it known that I, SAMUEL Cano'r, a citizen of the United States, residing at Boston, in the county of Suffolk and State of Massachusetts, have invented certain new and useful Improvements in the Manufacture of Carbonic- Acid Gas, of which the following is a specification, reference being had therein to the accompanying drawings.

The object of my invention is the production of carbonioacid gas in large quantities, of considerable purity, and at small cost. This gas is frequently made by the action of a strongeracid upon a carbonate, as in the manufacture of aerated waters; but in large manufacturing operat-ions-such as the recovery of sulphur from soda waste, the making of carbonate of magnesia, of bicarbonate of soda, and in the ammonia-soda processa much less costly method is indispensable. For this reason advantage has sometimes been taken of the fact that superheated steam passed over carbonate of lime while the latter is being heated causes a dislodgmcnt of carbonic-acid gas. In such cases, however, the products of combustion of the fuel and atmospheric air became mixed with the carbonic-acid gas and the ultimate product was more or less impure. Ithas also been suggested to first heat carbonate of lime in retorts by fire surrounding the latter, and then admit steam into the rctorts, which steam is superheated in the lower portions of the same and then rises into contact with the properly-heated carbonate of lime. By this process the ultimate product is obtained at a great and unnecessary expenditure of fuel, since the body of the retort must be heated to the same if not to a higher degree than the limestone. This process is also destructive to the apparatus, especially to the retorts, which are usually of cast-iron and are suspended from the top, and the great expense which this involves renders the process impracticable. I overcome these difficulties by the employment of my improved apparatus, by which I am enabled to apply the fire directly to the carbonate of lime within the retort or kiln, and I so manipulate the apparatus as to admit super heated steam after the fire has been removed. The carbonic-acid gas thus produced is exceedingly pure, the manipulation is simplified, and the process is rendered continuous.

The apparatus I employ consists, chiefly, of a peculiar]y-constructed limekiln managed in a peculiar way, to be detailed hereinafter.

Two of such kilns, forminga pair, are shown, the one in vertical elevation and the other, of identical construction, in vertical section in Figure 1. In Fig. 2 the same are shown in plan, as seen from above. Figs. 3, 4, 5, 6, and 7 show on a large scale certain details of con struction employed for closing the several openings of each kiln.

These kilns are charged from above with broken limestone, from which substance solely I obtain the carbonic-acid gas. The firing, in the construction shown, is effected by gas (preferably natural gas) emitted in large jets from an annular pipe, a", conducted from the gas-main ct. Air to sustain combustion is admitted at the openings b about the base of the kiln and at c. The tube a is also used for the admission of steam at the proper time from the piped, which leads from a superheater. The large pipe e issues from the upper part of the kiln and leads to an exhaust apparatusof any well-known construction, through which the carbon dioxide passes before use. Aheavy plate, f, covers the top or the kiln, and a door, of iron, g, closes the large opening below, through which the burned lime is raked out into trucks provided for that purpose. The precautions observed in closing these several openings will be referred to hereinafter.

The letters h, 2', j, and k refer to valves for controlling the flow of the gases.

The large pipe Z,with its connections, is that in which a condensation of water takes place, and is the main through which the pure carbon dioxide reaches the exhaustapparatus. (Erected at some distance, and not shown in the drawings.)

In carrying out my process one of these kilns is filled from above (the platef being dragged aside) with broken limestone, part of which, in the first instance,will fall through into the pit m below, it will not be subjected to the treatment under my process, and be finally raked out unchanged; but subsequent] y all the lime which lies upon the hearth will have been thoroughly calcined, and is removed only when a portion in the lower part of the shaft is ready to take its place. \Vhenever a lot of quick lime is removed below, a corresponding quantity of broken limestone is added above, so that the shaft remains always filled to the same extent, and the kiln works continuously. When a fresh descent of quicklime has taken place, the door 9 being tightly closed, the valves h and 7c are shut and z and j opened, whereby a flow of inflammable gas takes place fromthe openings (directedinward) in the annular pipe a where it is then to be ignited. The nozzle at it may be adjusted in position by the screw at 0. It enters, but does not close, the flared pipe below the valve 1', and consequentlythe gas, which is under considerable pressure, draws with it a large quantity of atmospheric air in the well-known way; but the annular space at a, about the nozzle n, is not large enough to admit so much air as to form an eX- plosive mixture with the inflammable gas, and the rest of the air necessary for perfect combustion enters through the openings 1). As the nozzle tube governed by the screw 0 swings sufficiently at a and the openings 1) are all'controlled by sliding plates, the combustion at the base of the kiln may be made perfect without a wasteful admission of air and without the formation of smoke. This firing is continued until the contents of the kiln, and especially those in its lower part, have been raised to a high temperature, and abundance of carbonic-acid gas with the other products of combustion make their appearance at the top of the shaft,

and discharge into the air through the open time the air-holes b, Fig. 1.

top of the kiln. The firing is now to be stopped by closing the valves 6 and j, and at the same f is to be drawn over the mouth of the kiln and cemented tight. The effect of the atmosphere of exceedingly hot steam which passes over the glowing limestone is, in accordance with a well-known law, to facilitate greatly the disengagement of the carbonic-acid gas, volumes of which in a condition of great purity will immediately make their appearance.

The kiln I have shown and described is so perfectlyinclosed with boilerironp,well bolted to a substantial bed-plate below, q, and to a flat continuous iron platform, 1', at the top, and its several openings admit of being closed and cemented so perfectly, that the exhaustpump in connection with the large pipe Z may be made to lower the atmospheric pressure within the kiln very considerably, whereby the evolution of the gas is promoted in a high degree. This feature of my process is an im; portant one, and it establishes a condition of things, when conjoined with the moving current of highly-superheated steam, which results not only in the abundant production of carbon dioxide, but also in the continuance of its disengagement when the temperature of the limestone has fallen very much lower than that at which the generation of gas ceases under ordinary circumstances.

To secure a supply of gas of the greatest purity, it is essential. that no fuel of any kind should remain in the kiln, and it is for this reason that illuminating-gas, water-gas, and

The heavy plate 7 support perfect combustion.

ing.

The chief adv vantage gained is the possibility of lowering greatly the pressure in the kiln; but its clos ing is almost equally important as the only way of insuring a pure gaseous product-that is, one free from atmospheric air. Before the exhaust apparatus is' started, through which the evolved carbonic-acid gas is removed, together with the steam which accompaniesit, the

mouth of the shaft above, d, the opening below from which the quicklime is raked, and the air-holes b have to be perfectly closed.

In Fig. 3 the heavy plate f is shown on an enlarged scale. This is undercut around its edge at s, and when it is in position thejoint between it and the platform-plate 1' is made perfect by ramming in asuitable cement (gem erally fire-clay) in a soft state all round, un-. der, and against the edge. This means of closing themouth of the kiln has to be perv petually repeated after every charge. It has the advantage of requiring no construction calculated to interfere with the work done upon the platform.

IOC

The door 9 is fully shown in Figs. 4,5, and

6 in front elevation, plan, and vertical crosssection. It will be seen to consist of a circular plate, 9, which covers a projecting rim, t, bolted to the iron casing of the kiln. The projection a on the plate 9 enters an annular recess, v,which is filled with suitable packing,

(not shown,) such as asbestus prepared for like uses. Vheh the clamping-screws w are entered and drawn up, this packing is compressed and a tight joint secured. By means of the small winch m, with its connectingchain, this heavy door may be readily lifted out of the way and as readily returned to its" place when required.

The three views embraced in Fig. 7 represent in front elevation, plan, and vertical cross-section the way in which I close the airholes I), and also, when desirable, adjust the volume of air which passes through them to A cast -iron ring, y, provided with the how a, is made fast to the outer shell of the kiln at each air-hole open- The flat segment I) swings on one leg of the bow in such a way that its faced surface lies upon the projecting faced surface of the ring y.

It is evident that by means of the clampingscrew 0 the segment b can be held over the air-hole,so as to cut off all or part only of the air, which would be drawn through the latter if fully open. Vhen the firing of a charge of limestone is in progress, the proper quantity of air can be determined by observing the character of the flame within thronghtheairholes.

\Vhen the temperature of the mass of glowing carbonate of lime falls to a certain extent under the action of the strongly-soperheated steam at low pressure, the disengagement of the gas will decrease, and finally cease. This fact is speedily made manifest by the change in the exhaust-tension exerted on the kiln by the exhaust-pump and indicated by its gage. \Vhen this point is rcached,the flow of steam must be stopped. If,then,the stratum 'of material acted upon in the lowerpartof the shaft has become good qnicklime,it is caused to fall upon the hearth m by raking out what is alreadybelow it; but if thelime is only partially burned, a second elevation of temperature by the combustion of gas, followed by the admission of steam, becomes necessary, so as to secure all the carbonic acid and obtain good caustic lime as a by-produot, the value of which is COllSlLlCl'tlbiB. The necessity for alternations of fire and steam will depend upon a number of variable circumstances, such as the quality of the limestone, of the inflammable gas used for fuel, the degree to which super heating is carried, and the intensity of the exhaust, &c. As the gaseous products from the kiln pass into the tube 2 and toward the exhaust apparatus,tl1ey should consist of carbonic'acid and the vapor of water only. To eliminate the latter, if that is desired, it is only necessary to adopt any one of the many well-known cooling methods by cont-act of cold water, by evaporation, or by simply making the pipe Z long enough and drawing from it the condensed water at a convenient place. This last is thcmethod presumed in the drawings, and it may in this connection be remarked that, in consequence of the very large amount of heat made latent by the disassociation of the carbonic acid and li1nc,thc gaseous mixture as it leaves the kiln will be, comparatively speaking, cool. The quantity of steam employed should also be as small as possible,aud at very low pressure, so that the actual amount of condensed water will be small.

The absence of common air, or nitrogen, or carbonic oxide from the gas I manufacture is a factof great-importance, for it is well known that at present the production of carbonic acid in large quantities from limestone and car bonaccous matter furnishes a gas diluted with many times its bulk of those impurities. Their presence and (in consequence of the room they occupy) the necessary enlargement and adaptation of the apparatus which deals with them for the sake of the available carbonic acid they contain add very decidedly to the cost of all technological operations based upon the ab sorption of the latter substance. This waste, depending on the presence of voluminous in1- purities, extends in some instances (as in the ammonia-soda process) to the loss of costly material, which passes oft with the uselessgases.

To make the dew of carbonic-acid gas by my process practically continuous, I employ two kilns, as in the drawings. These should be identical in construction and management; but they are used alternately as regards the intermittent heating and steaming of their contents-that is, while one is being fired up and is discharging into the air the other is receiving the superheated steanninto which the earbonic acid of the carbonate diifuses, and is dis charging into the main Z.

In this specification I have described a pair of kilns, each ofwhich runs continuously; but it is evident that the management of the kiln in this respect is not an essential part of my process, and that like results may be obtained when one or more kilns are used in which the whole charge of limestone is burned and emptied before fresh material is added. In such cases, however, it will sometimes be necessary to run more than two kilns in rotation, so as to gain time for emptying, recharging, and firing up. In this regard that manner of working my process which is most desirable will depend upon the nature of the demand for carbonic acid in the technical process for which it is madc-that is, whet-her it is wanting in very large quantities at intervals, or continuously and at a regular rate; and though in the foregoing I have spoken of gas as the fuel I employ, it is manifest that petrolcuni,&c.,can also be burned in the way now well understood and practiced for furnace fires, 0r,to state the case generally, any fuel may be used which after the requisite temperature has been reached can be totally cut off and excluded from the red-hot charge within the kiln, over which the superheated steam is to pass; and though I prefer the use of the perforated annular tube a both for gas and for steam as well, I do not regard that as the only good way of introducing those bodies into the kiln,for it is plain that they may be conducted to the proper place byindependent pipes, and

in like manner, though I believe the necessary supply of air to the kiln during the firing is best made by mixing part of it with the gas to be burned and supplying the rest as an atmosphere to support combustionstill very excellent results may be obtained by burning the gas without any such division of the total quantity of air; and though I have not shown or described any mechanical device-such as a blower or fan-to force gas or air into the kiln, I am fully aware that under certain circumst-ances such contrivances may be of great utility.

I do not claim, broadly, the application of steam for the dislodgment of carbonic acid.

In describing means for hermetically closing my kiln periodically I do not wish it to be understood that I regard the specific devices shown as the only ones suitable for the purpose, as there are an indefinite number of ways of doing the same thing satisfactorily. Some of these will cost less at first, but prove a source of constant expense in labor after wards; but choice in such matters will be governed by the requirements and conditions affecting each particular case.

To instance the modificationswhich may be made, it is sufficient to point out that by letting a collar of thin boiler-iron project from the shell of the kiln at a little distance from the air-hole opening the latter can be effectually closed at any time by the insertion of a thin circular plate bedded and covered with fireclay, and precisely the same principle may be applied to the large opening in the kiln from which the hot quicklime is discharged,

using a thin curved plate, if necessary, to suit the curve of the shell; but under these circumstances it is evident the dry and hardened cement has to be scraped away every time one part of my process gives place to the other, and While the exhaust is on the kiln attention has to be constantly paid to the joints to prevent the inward leak of air through cracks caused by drying.

The essential condition, which in my process is imperative in whatever way it maybe accomplished,is the possibility of absolutely closing the kiln, whereby atmospheric air is excluded and the requisite quantity of steam reduced to a minimum. This condition I be lieveit impossible to fulfill without giving the whole kiln everywhere a metal covering or shell such as I have described.

I am aware that plates and sheets of iron have been bolted to kilns and furnaces to give them strength and prevent dangerous fissures and cracks, and I do not claim, broadly, the ap plication of metal plates in the construction of limekilns.

What I do claim, and desire to secure by Letters Patent, is

1. The improvement in the art of making lime, the alternate treatment of said carbonate with the gaseous products of combustion at a high temperature and with superheated steam until its carbonic acid is expelled, substantially as and for the purpose describe 3; The improvement inthe art of making carbonic-acid gas, which consists in reducing the atmospheric pressure, and of maintaining this reduced pressure upon an incandescent mass of broken limestone pending the passage of superheated steam over the same, substantialiy as and for the purpose described.

4. In a limekiln for making carbonic acid, a perforated tube, as (6, adapted for distribut ing combustible gas and superheated steam alternately, connections thereof, respectively, with tubes conveying gas and steam, as a and (1, means for the intermittent admission of air when required to support combustion, and means for hermetically closing the kiln and for exhausting it when so closed by an air-pump or equivalent device, substantially as shown and described. p

In testimony whereof I affix my signature in presence of two witnesses.

SAMUEL CABOT. \Vitnesses:

Crras. P. NIcHoLs, T. F. ROBINSON. 

